JP2011526307A - Microstructures containing polyalkylnitrogen or phosphorus-containing fluoroalkylsulfonylonium salts - Google Patents

Abstract

  Films such as optical films that include a microstructured surface are described. The microstructure is a reaction product of a polymerizable resin composition containing a specific polyalkyl nitrogen or phosphorus-containing fluoroalkylsulfonyl onium salt as an antistatic agent. A polymerizable resin comprising at least one di (meth) acrylate monomer containing at least two aromatic rings, a reactive diluent, and a specific polyalkyl nitrogen or phosphorus-containing fluoroalkylsulfonyl onium salt as an antistatic agent is also used. be written.

Description

BACKGROUND ART Certain microstructured optical products, such as those described in US Patent Application Publication No. 2005/0148725, are commonly referred to as “brightness enhancement films”. Brightness-enhancing films are backlights such as liquid crystal displays (LCDs) including those used in electroluminescent panels, laptop computer displays, word processors, desktop monitors, televisions, video cameras, and automotive and airplane displays. In order to increase the brightness of the attached flat panel display, it is used in many electronic products.

  The brightness enhancement film desirably exhibits inherent optical and physical properties including the refractive index of the brightness enhancement film associated with the resulting brightness increase (ie, “gain”). The increase in brightness allows the electronic product to operate more efficiently by using less power to illuminate the display, thereby reducing power consumption and adding lower thermal load to its components, Extend product life.

  Brightness enhancing films have been prepared from polymerizable resin compositions containing high refractive index monomers that are cured or polymerized. In many cases, halogenated (eg brominated) monomers or oligomers are used to obtain a refractive index of, for example, 1.56 or higher. Another way to obtain a high refractive index composition is to use a polymerizable composition comprising high refractive index nanoparticles.

Problems to be solved by the invention
In one embodiment, a brightness comprising a polymerized microstructured surface, wherein the microstructure comprises a reaction product of a polymerizable resin composition comprising an antistatic agent having the general formula: Microstructured (eg, optical) films, such as enhancement films, are described.

_{^{R x JH 4-x + -}} A [SO 2 R f] m
Where
x is in the range of 3-4,
R is C ₁ -C ₁₂ alkyl group with or without independently catenary oxygen atoms or at least one hydroxyl end groups,
J is nitrogen or phosphorus,
A is nitrogen or carbon;
R _f is independently a fluorinated C ₁ -C ₄ alkyl group,
m is in the range of 2-3.

  The microstructure is typically disposed on a base film layer (such as a polarizing film) having a different composition than the microstructure (optionally primed).

  In such embodiments, the microstructure exhibits at least 90% cross-hatch adhesion to the base film layer.

In another embodiment, at least one di (meth) acrylate monomer containing at least two aromatic rings, a reactive diluent, the general formula _R x _JH ^4-x + - having _{A [SO 2} R _{f] m} A polymerizable resin composition comprising an antistatic agent (above) is described.

  In each of these embodiments, the antistatic agent may be present in an amount ranging from about 0.5 wt% to about 15 wt% solids, preferably from about 3 wt% to about 5 wt% solids. Furthermore, charge decay is preferably less than 1.5 seconds, more preferably less than 0.5 seconds when tested at 21.1 ° C. (70 ° F.) and 50% relative humidity.

The sum of R carbon atoms is at least 5, 6, 7 or 8. In some embodiments, x is 4 and the total number of R carbon atoms is at least 7. In some embodiments, the at least one Rf, is CF _3. In some embodiments, at least one R is methyl and the other R groups contain at least 2 carbon atoms. In other embodiments, x is 3 and each R contains at least 2 carbon atoms. In some embodiments, J is nitrogen. In other embodiments, J is phosphorus and x is 4.

  In one embodiment, R comprises a hydroxyl end group. The polymerizable resin composition preferably further comprises at least one (eg mono) carboxylic acid such as acrylic acid, methacrylic acid and mixtures thereof.

  Here, a (eg optical) film comprising a microstructured surface is described. The microstructure includes the reaction product of a polymerizable resin composition that includes a specific polyalkyl nitrogen or phosphorus-containing fluoroalkylsulfonyl onium salt as an antistatic agent.

The term “conductive” is often used in industry to refer to “static dissipative”, but these terms are not synonymous. Specifically, the conductive material has a surface resistivity of 1 × 10 ⁵ ohms / square or less, whereas the antistatic material typically has a surface of 1 × 10 ¹² ohms / square or less. It is considered to have a resistivity. The microstructured (eg, optical) film disclosed herein is at least about 1 × 10 ⁷ , 1 × 10 ⁸ , 1 × 10 ⁹ , 1 × 10 ¹⁰ ohm / square or 1 × 10 ¹¹ ohm / square. It exhibits a square surface resistivity and can still maintain antistatic properties.

  The optical films described herein typically comprise a (eg, preformed) light transmissive base (eg, film) layer and a light transmissive polymerized microstructured optical layer. Is done. The base layer and the optical layer can be formed from the same material, but are typically formed from different polymeric materials.

  As described in U.S. Pat. Nos. 5,175,030 (Lu et al.) And 5,183,597 (Lu), microstructured articles (e.g., brightness enhancement films) are (a) polymerizable. Preparing a composition; (b) depositing a polymerizable composition on the master negative microstructured molding surface in an amount barely sufficient to fill the cavity of the master; and (c) preformed. Filling the cavity by moving a bead of the polymerizable composition between a base (such as a PET film) and a master (at least one is flexible); and (d) curing the composition. Can be produced by a method including: The master may be made of a metal such as nickel, nickel-plated copper, or brass, or a thermoplastic material that is stable under polymerization conditions and preferably has a surface energy that allows the polymerized material to be cleanly removed from the master It may be.

  Useful base materials include, for example, styrene-acrylonitrile, cellulose acetate butyrate, cellulose acetate propionate, cellulose triacetate, polyethersulfone, polymethyl methacrylate, polyurethane, polyester, polycarbonate, polyvinyl chloride, polystyrene, polyethylene naphthalate. , Naphthalene dicarboxylic acid copolymers or blends, polycycloolefins, polyimides, and glasses. Optionally, the base material can include a mixture or combination of these substances. Further, the base may be multi-layered or may contain dispersed components suspended or dispersed in a continuous phase.

  In the case of microstructured products such as brightness enhancement films, examples of preferred base materials include polyethylene terephthalate (PET) and polycarbonate. Examples of useful PET films include photograde polyethylene terephthalate and MELINEX ™ PET (available from DuPont Films, Wilmington, Del.).

  Some base materials can be optically active and can act as polarizing plates. Polarization of light through the film can be achieved, for example, by the inclusion of a dichroic polarizer in the film material that selectively absorbs the passing light. The polarization of light is also achieved by incorporating inorganic materials such as aligned mica chips or by discontinuous phases dispersed in a continuous film, such as droplets of light-modulated liquid crystals dispersed in the continuous film. be able to. As an alternative, polarizing films can be prepared from microfine layers of different materials. The material in the film can be aligned to the polarization orientation, for example, by using methods such as stretching the film, applying an electric or magnetic field, and coating techniques.

  Examples of the polarizing film include those described in US Pat. Nos. 5,825,543 and 5,783,120. The use of these polarizing films in combination with brightness enhancing films is described in US Pat. No. 6,111,696. Another example of a polarizing film that can be used as a base is the film described in US Pat. No. 5,882,774.

  Useful substrates include: Vikuiti (TM) Dual Brightness Enhanced Film (DBEF), Vikuiti (TM) Brightness Enhanced (BEF), Vikiti (TM) Refrain P ESR), and commercially available optical films sold as Vikuiti (TM) Advanced Polarizing Film (APF), both of which are available from 3M Company.

  To facilitate adhesion of the optical layer to the base, one or more surfaces of the base film material can optionally be subjected to a primer treatment or other treatment. Particularly suitable primers for the polyester base film layer include sulfopolyester primers as described in US Pat. No. 5,427,835. The thickness of the primer layer is typically at least 20 nm and is generally 300 nm or less to 400 nm or less.

  The optical layer can have any number of useful patterns. These include regular or irregular prism patterns, which can be annular prism patterns, cube corner patterns or any other lenticular microstructure. A useful microstructure is a regular prism pattern that can act as a fully internal reflection film for use as a brightness enhancement film. Another useful microstructure is a corner cube prism pattern that can act as a retroreflective film or element for use as a reflective film. Another useful microstructure is a prism pattern that can act as an optical rotating film or element for use in an optical display.

  One preferred optical film having a polymerized microstructured surface is a brightness enhancement film. The brightness enhancement film generally enhances the on-axis brightness of the lighting device (referred to herein as “brightness”). Microstructure topography has multiple prisms on the film surface so that the film can be used to transfer light through reflection and refraction. The height of the prism is typically about 1 to about 75 microns. When used in an optical display such as that found in laptop computers, watches, etc., the microstructured optical film is in a pair of planes disposed at a desired angle from the normal axis penetrating the optical display, from the display. By limiting the dissipated light, the brightness of the optical display can be increased. As a result, light that will exit the display outside the acceptable range is reflected back to the display, where some of it is “reused” and returned to the microstructure film at an angle that can be emitted from the display. Can do. This reuse is useful because it can reduce the power consumption required to provide the desired brightness to the display.

  The microstructured optical layer of a brightness enhancement film generally includes a plurality of parallel longitudinal ridges that extend along the length or width of the film. These ridges can be formed from a plurality of prism vertices. Each prism has a first facet and a second facet. The prism is formed on a base having a first surface on which the prism is formed and a second surface that is substantially flat or planar and opposite the first surface. A right angle prism means that the apex angle is typically about 90 °. However, this angle may be in the range of 70 ° to 120 °, and may be in the range of 80 ° to 100 °. These vertices can be pointed, round, flat or truncated. For example, the ridges can be rounded to a radius in the range of 4-7-15 micrometers. The spacing (or pitch) between the prism vertices can be 5 to 300 micrometers. The prisms can be prepared in a variety of patterns, such as those described in US Pat. No. 7,074,463, which is incorporated herein by reference.

  For thin brightness enhancement films, the pitch is preferably 10-36 micrometers, more preferably 18-24 micrometers. This corresponds to a prism height of preferably about 5-18 micrometers, more preferably about 9-12 micrometers. The prism surfaces need not be the same, and the prisms may be inclined with respect to each other. The relationship between the total thickness of the optical article and the prism height may vary. However, it is typically desirable to use a relatively thin optical layer with a well-defined prism surface. For thin brightness enhancement films on substrates with a thickness of approximately 20-35 micrometers (1 mil), the ratio of prism height to total thickness is typically 0.2-0.4.

  The microstructured (eg, brightness enhancing film) described herein includes a polymerized microstructured surface (eg, a microstructured optical layer), where the microstructure includes an antistatic agent. The reaction product of the polymerizable resin composition is included.

  While various antistatic agents can provide static decay times of about 2-10 seconds (as measured according to the test methods described in the Examples), only certain types and amounts of antistatic agents are 1.5. It has been found that an electrostatic decay time of less than a second can be provided. Preferred antistatic agents provide static decay times of 0.5, 0.4, 0.3, 0.2 or 0.1 seconds or less.

  For embodiments in which the microstructure is disposed on a base layer such as a light transmissive (eg, polyester) film, the type and amount of antistatic agent is also determined by its presence in the polymerizable resin relative to the base film layer. It is selected so as not to impair the adhesion of the polymerized microstructure. The microstructure exhibits a cross-hatch adhesion of at least 80%, 85% or 90% to the base film layer (when measured according to the test method described in the examples). In the most preferred embodiment, the cross-hatch adhesion is 95-100%.

  The antistatic agent is preferably a polyalkylnitrogen or phosphorus-containing fluoroalkylsulfonylonium salt having the general formula:

_{^{R x JH 4-x + -}} A [SO 2 R f] m
Where
x is in the range of 3-4,
R is C ₁ -C ₁₂ alkyl group with or without a catenary oxygen atoms or hydroxyl terminal groups independently
J is nitrogen or phosphorus,
A is a nitrogen atom or a carbon atom,
R _f is independently a fluorinated C ₁ -C ₄ alkyl group,
m is in the range of 2-3.

  The total number of carbon atoms in the R group is generally at least 5. In some embodiments, the sum of R carbon atoms is at least 6, 7, or 8.

In embodiments where J is phosphorus, X is preferably 4. In some embodiments, x is 3 and each R contains at least 2 carbon atoms. For example, the antistatic _{^{agent, (C 2 H 5) 3}} NH + - N (SO 2 CF 3) 2, (C 2 H 5) 3 NH + - N (SO 2 C 4 F 9) 2, (C 2 _{^{H 5) 3 NH + - N}} (SO 2 CF 3) (SO 2 C 4 F 9), (C 2 H 5) 3 NH + - C (SO 2 CF 3) 3, (C 2 H 5) 3 NH _{^{+ - N (SO 2 C 2}} F 5) 2 , and may include the like.

In some embodiments, x is 4 and the total number of R carbon atoms is at least 7 or 8. For example, at least one R group can be methyl, the other three R groups contain at least two carbon atoms, which is for _{example, (C 2 H 5) 3} N (CH 3) + - N ( exemplified by _N (SO 2 _{CF 3) 2} and the like to these _{- SO 2 CF 3) 2,} (C 4 H 9) 3 N (CH 3) +.

Alternatively, all four R groups can be ethyl or butyl. For example, the antistatic ^{_{agent, (C 4 H 9) 4}} N + N (SO 2 CF 3) 2, (C 2 H 5) 4 N + - N (SO 2 CF 3) 2, (C 4 H 9) _{^{4 N + - C (SO 2}} CF 3) 3 and it may include the like.

Preferably at least one or two of the Rf groups are trifluoromethyl or trifluoroethyl. However, higher fluoroalkyl groups such as perfluorobutyl can also be used. For example, the antistatic _{^{agent, (C 2 H 5) 3}} NH + - N (SO 2 C 4 F 9) 2, (C 6 H 13) 4 N + - N (SO 2 C 2 F 5) 2, ( _{C 12 H 25) (CH 3} ) 3 N + - N (SO 2 C 2 F 5) 2 , and may include the like.

  In general, imide salts, i.e., where Q is nitrogen, are preferred over methide.

  In some embodiments, R preferably comprises at least one hydroxyl end group.

  Various mixtures of the polyalkyl nitrogen or phosphorus-containing fluoroalkylsulfonyl onium salts described herein can also be used.

  The total concentration of the polyalkyl nitrogen or phosphorus-containing fluoroalkylsulfonyl onium salt is preferably about 0.5 or 1% by weight of the polymerized microstructure, preferably in some embodiments 2 or 3% by weight, About 10, 11, 12, 13, 14 or 15% by weight or less. Concentrations of about 3 wt% to about 5 wt% have been found to provide favorable static decay characteristics, i.e., static decay of less than 0.5, 0.4, 0.3, 0.2 or 0.1 seconds. ing. In some embodiments, such as when an untreated polarizing base layer is used, typically less than 10% by weight polyalkyl to obtain at least 80 or 90% cross-hatch adhesion It is preferable to use a nitrogen- or phosphorus-containing fluoroalkylsulfonylonium salt.

  The polyalkyl nitrogen or phosphorus-containing fluoroalkylsulfonylonium salts described herein are either commercially available or can be synthesized by known techniques, as described in the art. For example, U.S. Pat. Nos. 6,924,329, 6,784,237, 6,740,413, 6,706,920, 6,592,988, Various patents and patent applications such as US 6,372,829 and US Patent Application Publication No. US 2003/114560 describe the synthesis of polyalkyl nitrogen or phosphorus containing fluoroalkylsulfonylimides and / or methides of onium salts.

  The polyalkyl nitrogen or phosphorus-containing fluoroalkylsulfonyl onium salt can be combined with various polymerizable resin compositions suitable for forming a microstructure, as is known in the art.

  The salt of the polyalkyl nitrogen or phosphorus-containing fluoroalkylsulfonylonium antistatic agent may be combined with a carboxylic acid prior to combining the bulk polymerizable resin composition and the antistatic agent salt to form a microstructure. . Representative examples include acrylic acid, methacrylic acid, and mixtures thereof. Various dicarboxylic acids are also speculated to be suitable. The dicarboxylic acid preferably has a relatively low molecular weight. The dicarboxylic acid may be linear or branched. Dicarboxylic acids having up to 6 carbon atoms between the carboxylic acid groups are preferred. These include, for example, maleic acid, succinic acid, suberic acid, phthalic acid, and itaconic acid.

  In some embodiments, the polymerizable resin composition includes surface-modified inorganic nanoparticles. In such embodiments, “polymerizable composition” refers to the total composition, ie, organic components and surface-modified inorganic nanoparticles.

  The organic component as well as the polymerizable composition are preferably substantially free of solvent. “Substantially solvent-free” is a polymerization having less than 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, and 0.5 wt% non-polymerizable (eg organic) solvent Refers to a sex composition. The solvent concentration can be determined by known methods such as gas chromatography (as described in ASTM D5403). A solvent concentration of less than 0.5% by weight is preferred.

  The constituent component of the organic component is preferably selected so that the polymerizable resin composition has a low viscosity. In some embodiments, the viscosity of the organic component is less than 1000 cps and typically less than 900 cps at the coating temperature. The viscosity of the organic component may be less than 800 cps, less than 700 cps, less than 600 cps, or less than 500 cps at the coating temperature. As used herein, viscosities (with shear rates up to 1000 sec-1) are measured on a 25 mm parallel plate using a Dynamic Stress Rheometer. Furthermore, the viscosity of the organic component is typically at least 10 cps, more typically at least 50 cps at the coating temperature.

  The coating temperature typically ranges from ambient temperature (25 ° C. (77 ° F.)) to 82 ° C. (180 ° F.). The coating temperature is less than 77 ° C (170 ° F), less than 71 ° C (160 ° F), less than 66 ° C (150 ° F), less than 60 ° C (140 ° F), less than 54 ° C (130 ° F), or It may be less than 49 ° C. (120 ° F.). The organic component can be a solid or can include a solid component, provided that the melting point of the polymerizable composition is lower than the coating temperature. The organic component described herein is preferably a liquid at ambient temperature.

  The organic component has a refractive index of at least 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60 or 1.61. The polymerizable composition comprising high refractive index nanoparticles can have a refractive index on the order of 1.70 (eg, at least 1.61, 1.62, 1.63, 1.64, 1.65, 1 .66, 1.67, 1.68 or 1.69). High transparency in the visible light spectrum is also typically preferred.

  The polymerizable composition is preferably energy curable on a time scale of less than 5 minutes (eg, for a brightness enhancement film having a thickness of 75 micrometers). The polymerizable composition is preferably sufficiently crosslinked to provide a glass transition temperature generally greater than 45 ° C. The glass transition temperature can be measured by methods known in the art such as differential scanning calorimetry (DSC), modulated DSC, or dynamic mechanical measurement. The polymerizable composition can be polymerized by conventional free radical polymerization methods.

  The polymerizable resin composition can include various aromatic monomers and / or oligomers. The polymerizable resin composition preferably contains at least one di (meth) acrylate monomer or oligomer containing at least two aromatic rings. Such di (meth) acrylate monomers typically have a molecular weight of at least 350 g / mol, 400 g / mol or 450 g / mol.

  Aromatic monomers or oligomers having at least two polymerizable (meth) acrylate groups may be synthesized or purchased. Aromatic monomers or oligomers typically contain a major portion of a specific structure, i.e. at least 60-70% by weight. It is generally recognized that other reaction products are typically present as by-products of the synthesis of such monomers.

  In some embodiments, the polymerizable composition comprises at least one aromatic (optionally brominated) bifunctional (meth) acrylate monomer that includes a major portion having the following general structure.

In the formula, Z is independently —C (CH ₃ ) ₂ —, —CH ₂ —, —C (O) —, —S—, —S (O) —, or —S (O) ₂ —. Each Q is independently O or S, and L is a linking group. L may independently comprise _C 2 _{-C 12} alkyl group branched or straight chain, n is in the range of 0. L preferably comprises a _C 2 -C ₆ alkyl group branched or straight chain. More preferably, L is C ₂ or C ₃ and n is 0, 1, 2 or 3. The carbon chain of the alkyl linking group may be substituted with one or more hydroxy groups. For example, L may be —CH ₂ CH (OH) CH ₂ —. Typically, the linking groups are the same. R1 is independently hydrogen or methyl.

  In some embodiments, the aromatic monomer is a reaction product of bisphenol di (meth) acrylate, ie, bisphenol A diglycidyl ether and acrylic acid. Although bisphenol A diglycidyl ether is generally more widely available, it is believed that other bisphenol diglycidyl ethers such as bisphenol F diglycidyl ether can also be used. For example, the di (meth) acrylate monomer can be a reaction product of tetrabromobisphenol A diglycidyl ether and acrylic acid. Such a monomer is available from UCB Corporation (Smyrna, GA) under the trade name “RDX-51027”. This material contains the main part of 2-propenoic acid, (1-methylethylidene) bis [(2,6-dibromo-4,1-phenylene) oxy (2-hydroxy-3,1-propanediyl)] ester. .

  One exemplary bisphenol-A ethoxylated diacrylate monomer is commercially available from Sartomer under the trade name “SR602” (reported to have a viscosity of 610 cps at 20 ° C. and a Tg of 2 ° C.). Another exemplary bisphenol-A ethoxylated diacrylate monomer is commercially available from Sartomer under the trade designation “SR601” (reported to have a viscosity of 1080 cps and a Tg of 60 ° C. at 20 ° C.).

  Alternatively, or in addition, the organic component may include one or more (meth) acrylated aromatic epoxy oligomers. Various (meth) acrylated aromatic epoxy oligomers are commercially available. For example, (meth) acrylated aromatic epoxies (described as modified epoxy acrylates) are available from Sartomer (Exton, PA) under the trade names “CN118” and “CN115”. (Meth) acrylated aromatic epoxy oligomers (described as epoxy acrylate oligomers) are available from Sartomer under the trade designation “CN2204”. Further, (meth) acrylated aromatic epoxy oligomers (described as epoxy novolac acrylate blended with 40% trimethylolpropane triacrylate) are available from Sartomer under the trade designation “CN112C60”. One exemplary aromatic epoxy acrylate is commercially available from Sartomer under the trademark “CN 120” (depending on the supplier, refractive index of 1.5556, viscosity of 2150 at 65 ° C., and Tg of 60 ° C. Have been reported).

  In some embodiments, the polymerizable resin composition includes at least one bifunctional biphenyl (meth) acrylate monomer that includes a major portion having the following general structure.

Wherein each R1 is independently H or methyl,
Each R2 is independently Br;
m is in the range of 0-4,
Each Q is independently O or S;
n is in the range of 0-10;
L is a C2-C12 alkyl group optionally substituted with one or more hydroxyl groups;
z is an aromatic ring, and t is independently 0 or 1.

In some embodiments, Q is preferably O. Further, n is typically 0, 1 or 2. L is typically C ₂ or C ₃ . Alternatively, L is typically hydroxyl substituted C ₂ or C ₃ . In some embodiments, z is preferably fused to a phenyl group, thereby forming a binapthyl core structure.

Preferably, at least one of -Q [L-O] n C (O) C (R1) = CH 2 group is substituted at an ortho or meta position. More preferably, the biphenyl di (meth) acrylate monomer comprises a sufficient amount of ortho and / or meta (meth) acrylate substituents such that the monomer is liquid at 25 ° C. In some embodiments, each (meth) acrylate group containing a substituent is attached to an aromatic ring group at the ortho or meta position. Ortho (meth) acrylate substitution with a majority amount of biphenyl di (meth) acrylate monomer (ie at least 50%, 60%, 70%, 80%, 90% or 95% of the substituents of biphenyl di (meth) acrylate monomer) Preferably it contains a group. In some embodiments, each (meth) acrylate group containing a substituent is attached to an aromatic ring group at the ortho or meta position. As the number of meta and especially para substituents increases, the viscosity of the organic component may increase as well. Furthermore, para-biphenyl di (meth) acrylate monomers are solid at room temperature and have little solubility (ie, less than 10%) even in phenoxyethyl acrylate and tetrahydrofurfuryl acrylate.

  Such biphenyl monomers are described in further detail in patent application No. 60/893953 (filed Mar. 9, 2007). Other biphenyl di (meth) acrylate monomers are described in the literature.

  The polymerizable resin composition may optionally include one or more (eg, monofunctional) (meth) acrylate diluents. The total amount of (meth) acrylate diluent can be at least 5%, 10%, 15%, 20%, or 25% by weight of the polymerizable composition. The total amount of (meth) acrylate diluent is typically 40% by weight or less, more typically about 35% by weight or less.

  In some embodiments, a multifunctional (meth) acrylate crosslinker may be used as a diluent. For example, tetraethylene glycol diacrylate, such as that sold by Sartomer under the trade name SR 268, has been found to be a suitable diluent. Other suitable multifunctional diluents include SR351, trimethylolpropane triacrylate (TMPTA).

  When one or more aromatic (eg monofunctional) (meth) acrylate monomers are used as diluents, such diluents can simultaneously increase the refractive index of the polymerizable resin composition. Suitable aromatic monofunctional (meth) acrylate monomers are typically at least 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57. Or a refractive index of 1.58.

  Aromatic (eg monofunctional) (meth) acrylate monomers typically contain phenyl, cumyl, biphenyl, or napthyl groups.

  Suitable monomers include phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 3-hydroxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate , Phenylthioethyl acrylate, 2-naphthylthioethyl acrylate, 1-naphthylthioethyl acrylate, naphthyloxyethyl acrylate, 2-naphthyloxyethyl acrylate, phenoxy-2-methylethyl acrylate, phenoxyethoxyethyl acrylate, 3-phenoxy-2 -Hydroxypropyl acrylate and phenyl acrylate.

  Phenoxyethyl acrylates include the trade name “SR339” from Sartomer, Eternal Chemical Co. Ltd .. Under the trade name “Etermer 210” and Toagosei Co. Commercially available from several sources, including the trade name “TO-1166” from Ltd. Phenylthioethyl acrylate (PTEA) is also commercially available from Cognis. The structures of these monomers are as shown below.

  In some embodiments, the polymerizable composition includes one or more monofunctional biphenyl monomers.

The polyfunctional biphenyl monomer is a terminal biphenyl group (where the two phenyl groups are not fused and joined by a bond) or a terminal group containing two aromatic groups joined by a linking group (eg Q). including. For example, when the linking group is methane, the end group is a biphenylmethane group. Alternatively, when the linking group is — (C (CH ₃ ) ₂ —, the end group is 4-cumylphenyl. A monofunctional biphenyl monomer is preferably one that is polymerizable by exposure to (eg, ultraviolet) radiation. Also containing an ethylenically unsaturated group, the monofunctional biphenyl monomer preferably contains one (meth) acrylate group or one thio (meth) acrylate group, with acrylate functionalities being generally preferred. The biphenyl group is directly bonded to the ethylenically unsaturated (eg (meth) acrylate) group, an exemplary monomer of this type is 2-phenyl-phenyl acrylate, biphenyl mono (meth) acrylate or biphenylthio The (meth) acrylate monomer is optionally substituted with one or more hydroxyl groups It may further comprise an alkyl group (for example of 1 to 5 carbons) A typical species of this type is 2-phenyl-2-phenoxyethyl acrylate.

  In one embodiment, a monofunctional biphenyl (meth) acrylate monomer having the following general formula is used.

Where R 1 is H or CH ₃ ;
Q is O or S,
n is in the range of 0-10 (eg, n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10);
L is preferably an alkyl group having 1 to 5 carbon atoms (ie methyl, ethyl, propyl, butyl or pentyl), optionally substituted with hydroxy.

  In another embodiment, the monofunctional biphenyl (meth) acrylate monomer has a structure of the general formula:

Where R 1 is H or CH ₃ ;
Q is O or S,
Z is _{- (C (CH 3) 2} -, - CH 2, -C (O) -, - S (O) - and -S _{(O) 2} - is selected from,
n is in the range of 0-10 (eg, n is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10);
L is an alkyl group having 1 to 5 carbon atoms (ie, methyl, ethyl, butyl or pentyl), optionally substituted with hydroxy.

  Toagosei Co. Ltd .. Some specific monomers commercially available from (Japan) include, for example, 2-phenyl-phenyl acrylate available under the trade name “TO-2344”, 4-(− 2-phenyl-2-propyl) phenyl acrylate and 2-phenyl-2-phenoxyethyl acrylate available under the trade name “TO-1463”.

  Various combinations of aromatic monofunctional (meth) acrylate monomers can be used. For example, a (meth) acrylate monomer containing a phenyl group may be used in combination with one or more (meth) acrylate monomers containing a biphenyl group. In addition, two different biphenyl (meth) acrylate monofunctional monomers may be used.

The polymerizable resin may contain up to 35% by weight of various other (eg non-halogenated) ethylenically unsaturated monomers. For example, when a structure (eg, prism) is cast on a preformed polycarbonate polymer film and photocured, the polymerizable resin composition has one or more N, N-disubstituted (meta). An acrylamide monomer may be included. These include N-alkyl acrylamides and N, N-dialkyl acrylamides, especially those containing C _1-4 alkyl groups. Examples are N-isopropylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-vinylpyrrolidone, and N-vinylcaprolactam.

  The polymerizable resin composition may optionally contain a non-aromatic crosslinking agent containing at least three (meth) acrylate groups at 20 wt% or less. Suitable crosslinking agents include, for example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (methacrylate), dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Trimethylolpropane ethoxylate tri (meth) acrylate, glyceryl tri (meth) acrylate, pentaerythritol propoxylate tri (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. Any one or combination of crosslinkers may be used. Since methacrylate groups tend to be less reactive than acrylate groups, the cross-linking agent preferably does not contain methacrylate functional groups.

  Various cross-linking agents are commercially available. For example, pentaerythritol triacrylate (PETA) is a trade name of “SR444” from Sartomer Company (Exton, Pa.) Under the name “Osaka Organic Chemical Industry, Ltd.”. (Osaka, Japan) under the trade name “Viscoat No. 300”, Toagosei Co. Ltd. (Tokyo, Japan) under the trade name “Aronix M-305”, and Eternal Chemical Co. , Ltd., Ltd. (Kaohsiung, Taiwan), commercially available under the trade name “Ethermer 235”. Trimethylolpropane triacrylate (TMPTA) is commercially available from Sartomer Company under the trade designation “SR351”. TMPTA is a trade name of “Aronix M-309” and manufactured by Toagosei Co., Ltd. Ltd .. It is also available from. Furthermore, ethoxylated trimethylolpropane triacrylate and ethoxylated pentaerythritol triacrylate are commercially available from Sartomer under the trade names “SR454” and “SR494”, respectively.

  In some embodiments, it is preferred that the polymerized microstructured surface of the optical film and the polymerizable resin composition be substantially free of bromine (ie contain less than 1% by weight). In other embodiments, the combined amount of bromine and chlorine is less than 1% by weight. In some embodiments, the polymerized microstructured surface or optical film and polymerizable resin composition are substantially non-halogenated (ie, less than 1% total bromine, chlorine, fluorine and iodine). Containing).

  The UV curable polymerizable composition includes at least one photoinitiator. One photoinitiator or a blend of photoinitiators may be used in the brightness enhancement film of the present invention. Generally, the photoinitiator is at least partially soluble (eg, at the processing temperature of the resin) and is substantially colorless after polymerization. If the photoinitiator is substantially colorless after exposure to a UV light source, the photoinitiator may be colored (eg, yellow).

  Suitable photoinitiators include monoacylphosphine oxide and bisacylphosphine oxide. Commercially available mono- or bis-acylphosphine oxide photoinitiators include 2,4,6-trimethylbenzoybiphenylphosphine oxide commercially available from BASF (Charlotte, NC) under the trade name “Lucirin TPO”; Further, ethyl-2,4,6-trimethylbenzoylphenyl phosphinate commercially available from BASF under the trade name “Lucirin TPO-L” and bis (available from Ciba Specialty Chemicals under the trade name “Irgacure 819”) 2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Other suitable photoinitiators include 2-hydroxy-2-methyl-1-phenyl-propan-1-one commercially available from Ciba Specialty Chemicals under the trade name “Darocur 1173”, as well as from Ciba Specialty Chemicals. , "Darocur 4265", "Irgacure 651", "Irgacure 1800", "Irgacure 369", "Irgacure 1700", and other photoinitiators commercially available under the trade names "Irgacure 907".

  The photoinitiator can be used at a concentration of about 0.1% to about 10% by weight. More preferably, the photoinitiator is used at a concentration of about 0.5 to about 5% by weight. An amount exceeding 5% by weight is generally disadvantageous in view of the tendency to cause yellowing of the brightness enhancement film. Other photoinitiators and photoinitiators may also be suitably used as determined by those skilled in the art.

  Surfactants such as fluorosurfactants and silicone surfactants reduce surface tension, improve wetting, enable smoother coatings, and reduce coating defects For this purpose, it can be optionally included in the polymerizable composition.

  In some embodiments, the polymerizable composition further comprises inorganic nanoparticles.

  Surface-modified (eg, colloidal) nanoparticles can be present in the polymerized structure in an amount effective to improve the durability and / or refractive index of the article or optical element. In some embodiments, the total amount of surface-modified inorganic nanoparticles can be present in the polymerizable resin or optical article in an amount of at least 10%, 20%, 30%, or 40% by weight. Since the polymerizable resin composition has a viscosity suitable for use in the casting and curing process of microstructured films, its concentration is typically less than 70% by weight and more typically 60% by weight. Is less than.

  The size of such particles is selected to avoid significant visible light scattering. It may be desirable to use a mixture of multiple types of inorganic oxide particles in order to optimize optical or material properties and reduce overall composition costs. The surface-modified colloidal nanoparticles can be oxide particles having a primary or associated particle size greater than 1 nm, 5 nm, or 10 nm (eg, non-associative). The primary or associated particle size is generally less than 100 nm, 75 nm, or 50 nm. Typically, the primary or associated particle size is less than 40 nm, 30 nm, or 20 nm. The nanoparticles are preferably non-associative. Those measurements may be based on transmission electron microscopy (TEM). Examples of the nanoparticles include metal oxides such as alumina, zirconia, titania, a mixture thereof, or a mixed oxide thereof. Surface-modified colloidal nanoparticles are substantially fully condensable.

  The crystallinity of fully condensed nanoparticles (with the exception of silica) (when measured as isolated metal oxide particles) is typically greater than 55%, preferably greater than 60%, more preferably 70%. Exceed. For example, the crystallinity can be in the range up to about 86% or more. The crystallinity can be determined by X-ray diffraction. Condensed crystalline (eg, zirconia) nanoparticles have a high refractive index, whereas amorphous nanoparticles typically have a lower refractive index.

  Zirconia and titania nanoparticles can have a particle size of 5 to 50 nm, or 5 to 15 nm, or 8 to 12 nm. Zirconia nanoparticles can be present in the durable article or optical element in an amount of 10-70 wt%, or 30-60 wt%. Zirconia used in the compositions and articles of the present invention can be obtained from Nalco Chemical Co. Under the trade name "Nalco OOSSOO8" and from Buhler AG Uzwil, Switzerland under the trade name "Buhler zirconia Z-WO sol".

  Zirconia particles can be prepared using hydrothermal techniques such as those described in US Pat. No. 7,241,437. The nanoparticles are surface modified. Surface modification involves modifying the surface properties by attaching a surface modifier to inorganic oxide (eg, zirconia) particles. The overall goal of surface modification of inorganic particles is to provide a resin with a low viscosity (eg using a casting and curing process) that can be prepared into a high brightness film, preferably with a homogeneous component. is there.

  Nanoparticles are often surface modified to improve compatibility with organic matrix materials. Surface-modified nanoparticles are often unassociated, non-agglomerated, or a combination thereof in the organic matrix material. The resulting light management films containing these surface-modified nanoparticles tend to have high optical transparency and low cloudiness. The addition of high refractive index surface-modified nanoparticles, such as zirconia, can increase the brightness enhancement film gain compared to films containing only polymerized organic materials.

  The monocarboxylic acid surface treatment agent preferably contains a compatibilizing group. A monocarboxylic acid can be represented by the formula AB, where the A group is a (zirconia or titania) group that can be attached to the surface of the nanoparticle (eg, a monocarboxylic acid), and B is a variety of different functionalities. It is a compatibilizing group containing. Carboxylic acid groups can be attached to the surface by adsorption and / or formation of ionic bonds. The compatibilizing group B is generally selected such that it is compatible with the polymerizable resin of the optical article (eg, brightness enhancement). The compatibilizing group B can be reactive or non-reactive and can be polar or non-polar.

  Examples of the compatibilizing group B that can impart a nonpolar property to the zirconia particles include linear or branched aromatic or aliphatic hydrocarbons. Representative examples of nonpolar modifiers having carboxylic acid functionality include octanoic acid, dodecanoic acid, stearic acid, oleic acid, and combinations thereof.

  The compatibilizing group B may optionally be reactive so that it is copolymerizable with the organic matrix of the optical article (eg brightness enhancement). For example, free radical polymerizable groups such as (meth) acrylate compatibilizing groups can be copolymerized with (meth) acrylate functional organic monomers to produce good, uniform brightness enhancing articles.

  Suitable surface modifications are described in U.S. Patent Application Publication No. 2007/0112097 and U.S. Patent Application No. 60/891812, filed February 27, 2007.

  The surface modified particles can be incorporated into the curable (ie, polymerizable) resin composition in a variety of ways. In a preferred embodiment, a solvent exchange procedure is utilized to disperse the particles in the polymerizable resin by adding the resin to the surface modified sol and then removing the water and cosolvent (if used) by evaporation. To the state. The evaporation step can be accomplished, for example, by distillation, rotary evaporation, or oven drying. In another embodiment, after surface modified particles are extracted into a water immiscible solvent, a solvent exchange can be performed if desired. Alternatively, another method of incorporating the surface-modified nanoparticles into the polymerizable resin involves adding the resin material in which the particles are dispersed after the modified particles are dried to a powder. The drying step in this method can be accomplished by conventional methods suitable for the system, such as oven drying or spray drying.

  A common measurement of such a light recycling effect is to measure the gain of the optical film. As used herein, “relative gain” is measured at the top of the light box as measured by the test method described in the Examples with the optical film (or optical film assembly) placed at the top of the light box. Defined as the on-axis brightness relative to the on-axis brightness measured in the absence of the optical film. This definition can be summarized by the following relationship:

  For the terms defined below, these definitions shall apply unless a different definition is given in the claims or elsewhere in the specification.

  The term “microstructure” is used herein as defined and explained in US Pat. No. 4,576,850. Therefore, it means a surface configuration that describes or characterizes a predetermined desired use or function of an article having a microstructure. Discontinuities such as protrusions and indentations on the surface of the article are drawn through the microstructure so that the sum of the area enclosed by the surface contour above the centerline is equal to the sum of the areas under the line. It is believed that the contour deviates from the average centerline, which is essentially parallel to the nominal surface (having the microstructure) of the article. For example, when measured with an optical or electron microscope through a typical characteristic length of a surface of 1-30 cm, the height of the deviation is typically about ± 0.005- ± 750 micrometers. . The average center line may be flat, concave, convex, aspheric or a combination thereof. Articles whose deviations are low, for example ± 0.005, ± 0.1, or preferably ± 0.05 micrometers, and that rarely or rarely occur in any deviation, i.e. any surface Articles without significant discontinuities are those in which the microstructure-bearing surface is essentially a “flat” or “smooth” surface, such articles being ophthalmic lenses, eg precision optical elements or It is useful as an element having a precision optical interface. Articles having an antireflection microstructure are examples of articles that have a low deviation and are frequently generated. A microstructure having a large number of the aforementioned deviations, for example, ± 0.1 to ± 750 micrometers, including a plurality of practical discontinuities that are the same or different and randomly or regularly spaced or continuous Articles that can contribute to such are retro-reflective corner cube sheeting, linear Fresnel lenses, video discs and brightness enhancement films. A surface having a microstructure can contain both low and high order practical discontinuities. Microstructured surfaces may contain extraneous or impractical discontinuities as long as the amount or type does not significantly interfere with or adversely affect the predetermined desired use of the article .

  “Refractive index” refers to the absolute refractive index of a material (eg, monomer) and refers to the ratio of the speed of electromagnetic radiation in free space to the speed of electromagnetic radiation in that material. The refractive index can be measured using known methods and is generally measured using an Abbe refractometer or Bausch and Lomb Refractometer (Catalog Number 33.46.10) (eg, commercially available from Fisher Instruments (Pittsburgh, PA)). It can be used and measured in the visible light region. It is generally recognized that the measured refractive index can vary to some extent depending on the instrument.

  “(Meth) acrylate” means both acrylate and methacrylate compounds.

  The term “nanoparticle” is defined herein to mean a particle (primary particle or associated primary particle) having a diameter of less than about 100 nm.

  “Surface-modified colloidal nanoparticles” refers to nanoparticles that each have a surface that is modified such that the nanoparticles provide a stable dispersion.

  As used herein, “stable dispersion” is allowed to stand for a period of time, eg, about 24 hours, under ambient conditions, eg, room temperature (about 20-22 ° C.), atmospheric pressure, and no excessive electromagnetic force. Later, it is defined as a dispersion in which colloidal nanoparticles are not suspected.

  The recitation of numerical ranges by endpoints includes all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5). ) Is included.

  As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the content clearly dictates otherwise. . Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. As used herein and in the appended claims, the term “or” is generally employed in its sense including “and / or” unless the content clearly dictates otherwise.

  Unless stated otherwise, it is understood that all numbers representing the amounts of ingredients, measurements of properties, etc. used in the specification and appended claims are modified in all examples by the term “about”. I want to be.

  The present invention should not be considered limited to the specific embodiments described herein, but, more appropriately, what is properly described in the appended claims defines all aspects of the present invention. It should be understood to include. Upon review of this specification, various modifications, equivalent methods, and numerous structures to which the present invention can be applied should be readily apparent to those skilled in the art of the present invention.

Test Method Cross Hatch Adhesion The adhesion of the microstructured resin layer to the base DBEF film was measured using a cross hatch test and 3M 610 cellophane® adhesive tape according to test method ASTM D3359.

  Adhesion is rated on a scale of 0-5, where 0 means 100% coating has been removed, while 5 means 0% coating has been removed (hence "4"). Is equivalent to about 80% fixing or 20% removal).

  Surface resistance was measured using a ProStat (Bensenville, IL) PRS-801 resistance system equipped with a PRF-911 concentric ring fixture. The surface resistance in ohms was converted to ohms / square by multiplying the measured value by 10 according to the instructions included with the instrument.

  The electrostatic charge decay time is measured by Electro-Tech Systems, Inc. Measurements were made using a model 406C static attenuator. This instrument charges the sample to 5 kV and measures the time required for the electrostatic charge to decay to 10% of its initial value. Some insulating samples do not fully charge up to 5 kV, which is noted as WNC in the data table.

Blooming test By placing a fine replication surface on a clean and untreated PET sheet, the tendency of the antistatic agent to move to the surface and transfer to another film was evaluated. The laminate was then placed between 0.32 cm (1/8 ") glass sheets held apart at an interval of 0.16 cm (1/16"). The panels were then placed in the chamber for 72 hours at 65 ° C. and 95% relative humidity. The polyester was then visually inspected for evidence of decolorization and transfer of antistatic additives. “P” indicates a pass rating or no transfer was observed, while “NP” indicates that residue was deposited on the PET.

Antistatic agent General chemical name (trade name, supplier)
1. Tributylmethylammonium bis (trifluoromethanesulfonyl) imide (available under the trade name “L-19055” from 3M Company (St. Paul, MN)),
Bis (trifluoromethanesulfonyl) imidolithium (available under the trade name “HQ-115” from 3M Company),
2. N, N-bis (2-hydroxyethyl) -N- (3′-dodecyloxy-2′-hydroxypropyl) methylammonium methosulfate (available from Cytec Industries under the trade name “Cyastat 609”;
3. Choline chloride is available from Aldrich Chemical Co. Obtained from

  4). N, N-diethylaminoethyl acrylate Q-salt, methosulfate (50% aqueous solution) was purchased from Monomer-Polymer & Dajac Labs, Inc, catalog number 8592.

  The other antistatic agents listed in Tables 1-3 were synthesized as described in the previously cited patents and patent applications.

  Two different base layer film substrates were used in the examples. The first substrate is a multi-layer optical film that is the same base layer film substrate as the brightness enhancement film commercially available from 3M Company under the trade name "Vikuiti (TM) DBEF II" (i.e., untreated). there were.

  The second substrate was a multilayer reflective polarizing optical film prepared according to Example 11 of US Pat. No. 6,352,761. The second substrate is a sulfone crosslinked with Cymel 327 melamine / formaldehyde resin as described in US 61/040737 (filed March 31, 2008) with a cured primer thickness of about 250 nm. Coated with modified polyester resin.

  The polymerizable resin is composed of 25 wt% phenoxyethyl acrylate and 75 wt% bisphenol A epoxy acrylate (CN120), with 0.5 wt% Darocur 1173 and 0.5 wt% TPO as photoinitiator. contains. The polymerizable resin is prepared by mixing 2 g of salt and 18 g of resin in an amber screw cap vial, sealing the vial, and heating the mixture in an oven at 90 ° C. for several minutes to remove the salt. By dissolving, it is modified using the salts shown in Tables 1-3. All salts except choline chloride dissolved readily and resulted in a clear modified resin after cooling to room temperature.

  The resin was applied to each substrate using the following procedure.

  1) Heat the resin at 60 ° C. for 1 hour until it liquefies.

  2) Heat the flat BEF tool on a hot plate at 71 ° C. (160 ° F.) for 1 minute to contact the substrate film to be coated.

  3) Heat the Catena 35 laminator to 71 ° C. (160 ° F.) and set the speed to 88.9 cm / min (35 inches / min).

  4) Apply resin bead line to the tool.

  5) Using a hand roller, place the substrate film gently against the tool, roll and stick it in place.

  6) The tool and the film sample are sandwiched between two large unprimed PET films to protect the roll of the laminator.

  7) Pass the sample through the laminator at the highest setting. This produces a nominal resin film thickness of 0.010 mm (0.4 mil).

  8) Pass the sample through a UV processor (UV Fusion Lighthammer, equipped with a D bulb, operating under nitrogen purge at 100% power and 9.14 m / min (30 ft / min) line speed).

  9) Slowly remove the film sample from the tool.

  All samples peeled easily from the tool.

  Allow the laminate to conditioned overnight at 21.1 ° C. (70 ° F.) / 50% RH in a constant temperature / humidity chamber, after which surface resistivity, static decay time and cross-hatch adhesion It took a measurement. The results are shown in Tables 1 to 3 below. For static decay measurements, the sample was oriented so that the microstructured prism array was located perpendicular or parallel to the test electrode.

    The laminate containing L-19055 was allowed to stand overnight at 22% RH in an ambient laboratory atmosphere. Re-measurement of electrostatic charge decay revealed that it did not change significantly, indicating that the antistatic system can work well even at low ambient humidity.

(Examples 2 to 6)
The procedure of Example 1 was repeated using the modified resin formulation shown in Tables 2-3. DBEF II was used as a substrate and the temperature was controlled at 68 ° C. After standing overnight at 21.1 ° C. (70 ° F.) / 50% RH in a constant temperature / humidity chamber, the laminate was subjected to measurement of static charge decay time. The results are shown in Tables 2-3.

  L-19055 shows the best combination of properties among the various salts tested and the best antistatic performance at low concentrations (<5 wt%) in the polymerizable resin. Also, the higher process temperature used in this example was necessary to obtain cured resin adhesion to the DBEF II substrate. At 60 ° C., the resin adhesion was poor.

  Other antistatic agents that have provided suitable combinations of charge decay and cross-hatch adhesion are shown as follows.

Counter ion heading:
Debutylimide = —N (SO ₂ C ₄ F ₉ ) ₂
Imide = —N (SO ₂ CF ₃ ) ₂
Methylbutylimide = —N (SO ₂ CF ₃ ) (SO ₂ C ₄ F ₉ )
BETI = —N (SO ₂ C ₂ F ₅ ) ₂
Methide = -C (SO ₂ CF ₃ ) ₃
A 10 g portion of N, N-diethylaminoethyl acrylate Q salt, methosulfate (50% aqueous solution) (purchased from Monomer-Polymer & Dajac Labs, Inc, catalog number 8592) was replaced with HQ115 (bis (trifluoromethanesulfonyl) imidolithium, And obtained in a screw cap vial with 6.0 g of an 80% by weight aqueous solution of 3M Company. & This slightly opaque mixture was extracted with 100 mL of dichloromethane, then the organic layer was separated and washed with two 50 mL portions of deionized water. Removal of the solvent and drying on a rotary evaporator left 4.2 g of a pale amber, slightly opaque liquid. Analysis of the product by proton and fluorine NMR showed that it was approximately 86.6% by weight hydroxyethyldiethylmethylammonium bis (trifluoromethanesulfonyl) imide and 2.6% by weight hydroxyethyldiethylammonium bis (trifluoromethanesulfonyl). Imide), 2.2% by weight acrylic acid, and 6.2% by weight methacrylic acid, the remainder being unidentified impurities. Using this antistatic agent, a brightness enhancement film for Example 18A in Table 4 was prepared.

Example 19A in Table 4, triethylammonium bis (perfluoroethanesulfonyl) _{^{imide, (C 2 H 5) 3}} NH + - N (SO 2 C 2 F 5) 2 was used as an antistatic agent, U.S. Patent 6,372 , 829 as described in Example 1 of Example 1.

  In either case, these antistatic agent compositions were combined with the polymerizable resin composition described above at the concentrations shown in Table 4 below. Next, this resin composition was prepared as a brightness enhancement film as described above using “Vikuiti (trademark) DBEF II” as a base material. The test results were as follows.

Claims (28)

Containing polymerized microstructured surface, a brightness enhancement film, the microstructure general formula _{^{R x JH 4-x + -}} A [SO 2 R f] m
A reaction product of a polymerizable resin composition comprising an antistatic agent having the formula:
x is in the range of 3-4,
R is C ₁ -C ₁₂ alkyl group with or without independently catenary oxygen atoms or at least one hydroxyl end groups,
J is nitrogen or phosphorus,
A is nitrogen or carbon;
R _f is independently a fluorinated C ₁ -C ₄ alkyl group,
m is a brightness enhancement film in the range of 2-3.   The brightness enhancement film of claim 1, wherein the antistatic agent is present in an amount ranging from about 0.5 wt% to about 15 wt% solids.   The brightness enhancement film of claim 1, wherein the antistatic agent is present in an amount ranging from about 3 wt% to about 5 wt% solids.   4. A brightness enhancement film according to any one of the preceding claims, wherein the charge decay is less than 1.5 seconds when tested at 21.1 [deg.] C (70 [deg.] F) and 50% relative humidity.   The brightness enhancement film of any one of claims 1 to 3, wherein the charge decay is less than about 0.5 seconds when tested at 21.1 ° C (70 ° F) and 50% relative humidity.   The brightness enhancement film according to claim 1, wherein the microstructure is disposed in a base film layer having a composition different from that of the microstructure.   The brightness enhancement film according to claim 6, wherein the base film layer further comprises a primer.   The brightness enhancement film according to claim 6 or 7, wherein the base film layer contains polyester.   The brightness enhancement film according to claim 8, wherein the base film layer is a polarizing film.   The brightness enhancement film according to claim 8 or 9, wherein the primer contains a sulfonated polyester.   The brightness enhancement film according to any one of claims 6 to 10, wherein the microstructure exhibits at least 90% cross-hatch adhesion to the base film layer.   The brightness enhancement film according to any one of claims 1 to 11, wherein the total number of carbon atoms of R is at least 5.   13. The brightness enhancement film according to claim 12, wherein x is 4 and the total number of R carbon atoms is at least 7. At least one Rf is CF _3, brightness enhancement film according to claim 12 or 13.   15. A brightness enhancement film according to any one of claims 12 to 14, wherein at least one R is methyl and the other R groups contain at least two carbon atoms. The antistatic _{agent, (C 2 H 5) 3} N (CH 3) + - N (SO 2 CF 3) 2, (C 4 H 9) 3 N (CH 3) + - N (SO 2 CF 3) The brightness enhancement film according to claim 15, which is selected from the group consisting of ₂ and a mixture thereof.   The brightness enhancement film of claim 12, wherein x is 3 and each R contains at least 2 carbon atoms. The antistatic _{^{agent, (C 2 H 5) 3}} NH + - N (SO 2 CF 3) 2, (C 2 H 5) 3 NH + - N (SO 2 C 4 F 9) 2, (C 2 H _{^{5) 3 NH + - N (}} SO 2 CF 3) (SO 2 C 4 F 9), (C 2 H 5) 3 NH + - C (SO 2 CF 3) 3, (C 2 H 5) 3 NH + _{^{- N (SO 2 C 2 F}} 5) is selected from ₂ and mixtures thereof, the brightness enhancing film of claim 17.   The brightness enhancement film according to claim 12, wherein x is 4 and the total number of carbon atoms in R is at least 8. The antistatic _{^{agent, (C 4 H 9) 4}} N + - N (SO 2 CF 3) 2, (C 2 H 5) 4 N + - N (SO 2 CF 3) 2, (C 4 H 9) _{^{4 N + - C (SO 2}} CF 3) 3, (C 6 H 13) 4 N + - N (SO 2 C 2 F 5) 2, (C 12 H 25) (CH 3) 3 N + - N ( brightness enhancement film according to SO ₂ C ₂ F _{5) 2} is selected from the group consisting of mixtures according to claim 19.   The brightness enhancement film according to any one of claims 1 to 20, wherein J is nitrogen.   The brightness enhancement film according to any one of claims 1 to 21, wherein J is phosphorus and x is 4.   23. A brightness enhancement film according to any one of claims 1 to 22, wherein R comprises at least one hydroxyl end group.   The brightness enhancement film according to any one of claims 1 to 23, wherein the polymerizable resin composition further comprises at least one carboxylic acid.   The brightness enhancement film according to claim 24, wherein the polymerizable resin comprises at least one monocarboxylic acid.   26. The brightness enhancement film according to claim 25, wherein the monocarboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, and mixtures thereof. At least one di (meth) acrylate monomer containing at least two aromatic rings, a reactive diluent, the general formula _{^{R x JH 4-x + -}} A [SO 2 R f] m
(Where
x is in the range of 3-4,
R is C ₁ -C ₁₂ alkyl group with or without independently catenary oxygen atoms or at least one hydroxyl end groups,
J is nitrogen or phosphorus,
A is a nitrogen atom or a carbon atom,
R _f is independently a fluorinated C ₁ -C ₄ alkyl group,
and m is in the range of 2 to 3). Containing polymerized microstructured surface, a microstructured film article, the microstructure general formula _{^{R x JH 4-x + -}} A [SO 2 R f] m
(Where
x is in the range of 3-4,
R is C ₁ -C ₁₂ alkyl group with or without a catenary oxygen atoms or hydroxyl terminal groups independently
J is nitrogen or phosphorus,
A is a nitrogen atom or a carbon atom,
R _f is independently a fluorinated C ₁ -C ₄ alkyl group,
A microstructured film article comprising a reaction product of a polymerizable resin composition comprising an antistatic agent having m ranging from 2 to 3.